Method of treating hydrocarbons



March 31, 1936. J c, MORRELL METHOD OF TREATING HYDROCARBONS Filed Nov. 29, 1933 JZ/ IZZ OK' JEz ae C. Morrell 55/ Z66 Patented Mar. 31, 1936 PATENT OFFICE 2,035,910 METHOD OF TREATING HYDROCARBONS Jacque C. Morrell, Chicago, Ill., assignor to Universal Oil Products Company, Chicago, 111., a corporation of Delaware Application November 29, 1933, Serial No. 700,231

4 Claims.

This application is a continuation in part of my application Serial No. 409,433 filed November 25, 1929.

This invention relates to the treatment of mixtures of hydrocarbon and bituminous materials, particularly coals, and also lignite, peat, pitches, grahamite, albertite and others, and more particularly relates to the production from such mixtures of hydrocarbons and bituminous materials of lower boiling hydrocarbons suitable as motor fuels by cracking or thermal decomposition of the hydrocarbons and the bituminous materials, producing at the same time coke, gas, and other valuable by-products. a

In carrying out the process of the invention, a mixture of oil and coal or other bituminous material is made preferably by suspending the latter in the oil in a finely divided state and then subjecting the mixture to heat treatment whereby the mixture is brought to the cracking or conversion temperature, thereby producing low boiling products suitable as motor fuels.

The product so produced possesses high antiknock properties as a motor fuel owing to the cracking of the material distilled from the bituminous substances or which are cracked in situ to produce low boiling products suitable as motor fuel and containing ahigh percentage of aromatic and unsaturated hydrocarbons which are 0 known to possess high antiknock properties.

In onespecific embodiment the invention comprises the introduction of oxygen or a gas containing free oxygen or ozone, such as air, or mix-- tures of gases comprising free oxygen, as well 5 as inert gases such as flue gas, nitrogen, carbon dioxide with air and oxygen or ozone, into the system where the mixture of hydrocarbon oil and bituminous material, for example coal, are undergoing treatment to partially oxidize the mixture,

l particularly the suspended bituminous material. Preferably the degree of oxidation is such that intermediate compounds are formed, such as organic acids, aldehydes, ketones and alcohols, and in order to assist in the control both of the rate and kind of reaction, I may introduce catalysts such as metals, metallic oxides or salts of metals, for example, calcium, aluminum, zinc, tin, iron, nickel, lead, copper, and others, and their oxides and salts.

In order to illustrate the operation I will refer to the accompanying drawing:

Raw oil comprising ,a. fraction of petroleum, coal tar and the like, admixed with coal or other bituminous materials such as those mentioned, the latter preferably being suspended in the oil cleaned out or a t in a finely divided condition, is pumped by means of pump I through line 2 and valve 2' into line 3, where it meets the reflux from hot oil pump 4 entering line 3 and is passed into the heating coil 5 located in furnace 6, wherein the mixture is 5 brought to the conversion temperature. A portion of the raw oil may be pumped from pump 1 into line 2 through control valve 3, or it may be pumped through line 1' controlled by valve 7" into dephlegmator or fractionator i8, where 0 it receives heat from the vapors rising in dephlegmator l8, and the catalyst, where used, may be mixed preferably in a finely divided state with the rawoil passing through pump 1 or with the mixture of the raw oil and bituminous material 15 passed through pump I.

- Air or oxygen, or other gases containing free oxygen, are pumped by means of pump or compressor 8 through line 9 and valve 9' into line 3, passing with the mixture of hydrocarbon oil and bituminous material, which mixture may or may not contain a catalyst, into the heating coil wherein some conversion into lower boiling products and into intermediate oxidation products occurs. The material leaving heating coil 5 passes 25 through vapor line I0 controlled by valve ll into reaction chamber I2. Any non-vaporized material deposited in this chamber is withdrawn through line l3 controlled by valve l3. The coke produced as a result of the treatment accumulates in reaction chamber I2 and may be removed by any of the well known means. I may use several reaction chambers to provide -for the operation of one while the other is being rd is being prepared for operation. I may also provide for the introduction of air or oxygen, or other gases containing free oxygen, into the reaction chamber through line H controlled by valve I4 and the oxygen containing gas may be introduced at various levels in the chamber through valved connections IS. The vapors leaving reaction chamber l2 pass through vapor line l6 controlled by valve l1 and enter dephlegmator I8. The reflux condensate resulting from the condensation of heavier porvtions of the vapors entering dephlegmator l8 passes through line l8 and valve 4 to hot ofl pump 4, the said reflux condensate being then returned to the heating coil 5 for further conversion. It is to be pointed out particularly that the retreatment of the partially oxidized reflux condensate produces a motor fuel product which is superior in antiknock properties to the retreatment of reflux condensate not subjected to the 55 tor fuel produced coal and oil cited, charged, will be approximately 120 pounds per free oxygen,

action of a gas containing free oiwgen under cracking conditions. The vapors leaving dephlegmator l8 pass through line is controlled by valve It into cooler and condenser 20 controlled by valve 20, the liquid products being collected into receiver 2i. The gas passes through line 22 controlled by valve 22 and the liquid product is withdrawn through line 23 cbntrolled by valve 24.

As an illustration of the results obtained by the process of my invention, a mixture containing per cent by weight of a 26 A. P. I. gra 'ty topped Mid-Continent crude oil and 20 per cent by weight of a West Virginia bituminous coal when treated at a pressure of approximatelyBOO pounds per square inch and a temperature of 925 F. using -5 per cent by weight of air will result in the production of approximately '75 per cent of distillate based on the volume of the oil charged containing approximately '75 per cent of motor fuel, making a total of approximately 56 per cent of motor fuel based on the oil charged. The mowas equivalent in antiknock value to approximately 35 per cent benzol mixed with a straight-run Pennsylvania gasoline.

The total coke produced from the mixture of based on the volume of oil barrel. A substantial percentage of hydrocarbon oxidation products will be present in the distillate, adding to its antiknock properties. The coke produced by the process is of high quality having a calorific value of approximately 14,500 B. t. u. s per pound and is generally honeycomb in structure. I

The gas produced by the process makes a very good fuel of high calorific value and may be utilized for purposes other than fuel.

Other types of hydrocarbon oils may also be employed in admixture with the bituminous coal, for example, crude oilsor fractions thereof generally, including asphaltic base crudes: such as those from California, Mexico and the like. Coal tars and lignite tars may also be employed as the hydrocarbon component, although it is to be understood that somewhat difierentproducts will be obtained when these tars are employed than when petroleum fractions are employed.

Increasing the amount of air or gas containing and suitably regulating the conditions, will permit control of the process to produce substantial yields of select products of partial oxidation such as those hereinbefore referred to, including alcohols, aldehydes, ketones and acids. a

The process may be operated at various ternperatures and pressures, for example, from 750 F. .to 1000 F., more or less, and in general a cracking temperature, and from 50 pounds per square inch pressure up to 1500 pounds per square inch, more or less. Generally speaking, lower temperatures and pressures may be used in the presence of catalysts.

While I have given specific examples of the yields obtained by the process, it may be readily recognized that the results obtained will depend upon the operating conditions which may be varied over a wide range, and the examples given treated mixture.

are for illustrative purposes only and not in a limiting sense.

I-claim as my invention:

1. A. process for producing antiknock motor fuel which comprises mixing finely divided solid bituminous material with hydrocarbon oil, passing the mixture in a restricted stream through a heating zone and then discharging the same into an enlarged zone, heating the mixture to a gasoline-producing cracking temperature under pressure in the heating zone and effecting substantial cracking igiereof into gasoline, introducing to the mixture passing through the heating zone a gas containing free oxygen in suificient quantity to form condensable partial oxidation products, separating vapors from residue in the enlarged zone, and condensing the vapors evolved from the thus treated mixture.

2. A process for producing antiknock motor fuel which comprises mixing finely divided coal with hydrocarbon oil, passing the mixture in a restricted stream through a heating zone and then discharging the same into an enlarged zone, heating the mixture to a gasoline-producing cracking temperature under pressure in the heating zone and effecting substantial cracking thereof into gasoline, introducing to the mixture passing through the heating zone a gas containing free oxygen in 'sufilcient quantity to form condensable partial oxidation products, separating vapors from residue in the enlarged zone, condensing the vapors eolved from the thus 3. A process for producing antiknock motor fuel which comprises mixing finely divided coal with hydrocarbon oil, passing the mixture in a restricted stream through a heating zone and then discharging the same into an enlarged zone, heating the mixture to a gasoline-producing cracking temperature under pressure in the heating zone and effecting substantial cracking thereof into gasoline, introducing to the mixture passing through the heating zone a gas containing free oxygen in suiiicient quantity to form condensable partial oxidation products, separating vapors from residue in the enlarged zone, fractionating the vapors and returning the reflux condensate produced thereby for further treatment, and condensing the vapors evolved from the thus treated mixture.

4. A process for producing antiknock motor fuel which comprises mixing finely divided solid bituminous material with hydrocarbon oil', passing the mixture in a restricted stream through a heating zone and then discharging the same into an enlarged zone, heating the mixture to a 

